EP0349419B1 - Verfahren zur Herstellung eines Katalysators, verwendbar für die oxydierende Umwandlung von Methan in hohe Kohlenwasserstoffe - Google Patents

Verfahren zur Herstellung eines Katalysators, verwendbar für die oxydierende Umwandlung von Methan in hohe Kohlenwasserstoffe Download PDF

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Publication number
EP0349419B1
EP0349419B1 EP89401840A EP89401840A EP0349419B1 EP 0349419 B1 EP0349419 B1 EP 0349419B1 EP 89401840 A EP89401840 A EP 89401840A EP 89401840 A EP89401840 A EP 89401840A EP 0349419 B1 EP0349419 B1 EP 0349419B1
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process according
cations
coprecipitate
metals
aqueous phase
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French (fr)
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EP0349419A1 (de
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Christian Forquy
Didier Résidence le Vallon des Sources Tichit
Didier Anglerot
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Societe National Elf Aquitaine
Elf Aquitaine Norge AS
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Societe National Elf Aquitaine
Elf Aquitaine Norge AS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/232—Carbonates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S585/00—Chemistry of hydrocarbon compounds
    • Y10S585/929—Special chemical considerations
    • Y10S585/943—Synthesis from methane or inorganic carbon source, e.g. coal

Definitions

  • the invention relates to a process for the preparation of a catalyst capable of promoting the oxidative conversion of methane to C hydrocarbons. + 2 with high activity and selectivity.
  • the citation DE-A-3237079 suggests using a catalyst based on PbO and Si O2 and the citation EP-A-0196541 describes the use of a Li / MgO catalyst, in the formulation from which lithium is generally introduced in the form of carbonate.
  • Such catalysts quickly lose their activity at the temperatures necessary to activate methane, which are of the order of 750 ° C., since at these temperatures PbO is eliminated by sublimation and the lithium carbonate is unstable and decomposes.
  • the citation WO-A-86/07351 proposes to carry out the conversion of methane in the presence of oxygen by using a catalyst based on rare earth oxides doped by addition of metal oxides of groups IA and IIA of the Periodic Table Elements, which makes it possible to work with spatial speeds of the methane / oxygen mixture significantly higher than those provided for in the citation EP-A-0189079 and to achieve higher rates of conversion of methane with improved selectivities to hydrocarbons.
  • the invention therefore provides a particular process for the preparation of a catalyst containing at least one metal from the lanthanide group and at least one alkaline earth metal, which makes it possible to obtain a particularly active and selective catalyst in the oxidative conversion of methane to higher hydrocarbons and in particular C hydrocarbons + 2 .
  • the method according to the invention is characterized in that an aqueous phase is brought into contact containing in solution cations of at least one metal from the group of lanthanides and of at least one alkaline earth metal with a sufficient amount of a source of carbonate ions and optionally of a source of hydroxide ions to form a coprecipitate of carbonates or / and hydroxycarbonates of said metals containing at least 5% by weight of carbonates and bring the pH of the reaction medium resulting in a value greater than 8, the coprecipitate is separated from the reaction medium and subjected said coprecipitate to washing and then to drying and the washed and dried coprecipitate is subjected to calcination at a temperature between 400 ° C. and 1000 ° C.
  • said reaction medium containing the coprecipitate is maintained at a temperature ranging from 60 ° C. to 150 ° C. for a period of between 30 minutes and 30 hours and preferably between 2 hours. and 8 p.m.
  • the metals of the lanthanide group capable, according to the invention, of providing a part of the cations in solution in the aqueous phase are the metals of the Periodic Table of the Elements having the atomic numbers 57 and 59 to 71, said metals being in particular such as lanthanum , praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, erbium, holmium, thulium, ytterbium and lutetium.
  • the alkaline earth metals capable, according to the invention, of providing the cations associated with the cations of the metal or metals of the lanthanide group are the metals of group IIA of the Periodic Table of the Elements including berylliun, magnesium, calcium, strontium and barium.
  • the respective proportions of cations of the metal (s) from the lanthanide group and cations of the alkaline earth metal (s) in the aqueous phase can vary quite widely.
  • Cations of one or more metals other than the metals of the lanthanide group and the alkaline earth metals, in particular scandium, yttrium, lithium, may also be present in the aqueous phase in addition to the cations of the alkaline earth metals and cations of the group lanthanides.
  • the amount of these additional cations represents up to 30% and preferably up to 15% of the overall weight of the cations originating from the metal (s) from the lanthanide group and from the alkaline earth metal (s).
  • the source of the cations present in the aqueous phase consists of water-soluble compounds, for example chlorides, of the metals mentioned above.
  • the source of carbonate ions can be chosen from the various carbonates which are water-soluble at the concentrations used, in particular carbonates of alkali metals such as sodium carbonate and potassium carbonate, ammonium carbonate, quaternary ammonium carbonates.
  • the source of hydroxide ions can be chosen from the various hydroxides which are water-soluble at the concentrations used, in particular hydroxides of alkali metals such as sodium and potassium hydroxides, or alternatively quaternary ammonium hydroxides.
  • the proportion of source of carbonate ions used alone or the respective proportions of the sources of carbonate ions and hydroxide ions are in particular chosen so that the coprecipitate resulting from the contacting of said carbonate or carbonate ions and hydroxides with the cations present in the aqueous phase contains, by weight, 5% to 100% of carbonates and that the pH of the reaction medium is brought to a value ranging from 9.5 to 13.5.
  • the contacting of the cations present in the aqueous phase with the carbonate ions or with the carbonate ions and the hydroxide ions giving rise to the coprecipitate of carbonates or carbonates and of hydroxycarbonates can be carried out in any suitable manner.
  • the source of carbonate ions when used alone, can be added, in aqueous solution, to the aqueous phase containing the cations, said addition being able to be carried out in one or more fractions or alternatively continuously.
  • the source of hydroxide ions and the source of carbonate ions can be added, in aqueous solution, either successively or as a mixture. or alternatively simultaneously and separately, to the aqueous phase containing the cations, each addition being able to be carried out in one or more fractions or alternatively continuously.
  • An advantageous way of bringing the cations present in the aqueous phase into contact with the carbonate ions or with the carbonate ions and the hydroxide ions giving rise to the coprecipitate consists in continuously mixing the aqueous phase containing the cations with an alkaline aqueous phase containing in solution either the source of carbonate ions or the source of carbonate ions and the source of hydroxide ions, at appropriate concentrations, by controlling the flow rates of the aqueous phases brought into contact so that the coprecipitate formed contains at least 5% by weight of carbonates and that the pH of the reaction medium formed is maintained at a substantially constant value throughout the co-precipitation, said value being greater than 8 and preferably ranging from 9.5 to 13.5.
  • the calcination of the dried coprecipitate is carried out by heating said coprecipitate at temperatures between 400 ° C and 1000 ° C as indicated above and preferably ranging from 450 ° C to 800 ° C, said heating being able to be carried out in air or in inert atmosphere.
  • the calcined coprecipitate is shaped by any known technique, for example by a tableting technique, to constitute the catalyst which can be used in catalytic reactors.
  • the product is a particularly active and selective catalyst for the conversion of methane, in the presence of oxygen, to higher hydrocarbons and in particular to C hydrocarbons. + 2 .
  • the methane which is subjected to the oxidative catalytic conversion can be pure methane or even methane containing up to 10% by volume of ethane as is the case for industrial natural gas.
  • the oxygen reacted with methane is preferably pure oxygen, since the use of air as a source of oxygen, although possible, requires separation of the nitrogen before recycling the unconverted methane.
  • Methane and oxygen can be brought into contact with the catalyst either in the form of separate streams or in the form of a preformed mixture.
  • the amounts of methane and oxygen brought into contact are such that the molar ratio of methane to oxygen has a value ranging from 1 to 20 and preferably from 2 to 10.
  • the catalyst prepared according to the invention makes it possible to carry out the methane conversion reaction at temperatures between 600 ° C. and 1100 ° C. without decomposition of the catalyst.
  • Preferred temperatures according to the invention for this reaction range from 700 ° C to 900 ° C.
  • the pressures which can be used for carrying out said reaction are not critical. They may in particular be between approximately 1 and approximately 50 bars and preferably be between 1 and 20 bars.
  • the space velocity of the gas mixture of methane and oxygen in contact with the catalyst can, according to the invention, have a value between 3 and 1000. Space velocities preferred values range from 5 to 300.
  • An aqueous solution of barium cations and lanthanum cations was prepared by dissolving 0.25 mole of BaCl2, 2H2O and 0.125 mole of LaCl3, 6H2O in 1 liter of distilled water and the solution obtained was placed in a 2 l flask swept by a stream of nitrogen.
  • an aqueous solution containing 0.25 M / l of Na OH and 0.25 M / l of Na2CO3 was added dropwise so as to precipitate the barium and lanthanum cations in the form of a carbonate and hydroxycarbonate coprecipitate, the rate of addition of said solution being adjusted to obtain, after an addition period of 2 hours, a reaction medium having a pH equal to 10.
  • the resulting reaction medium, containing the coprecipitate formed was then brought to 90 ° C. and maintained at this temperature, still with stirring, for a period of 16 hours.
  • the coprecipitate was then separated from the reaction medium by filtration, then washed with distilled water until complete elimination of the chlorides and finally dried at 60 ° C.
  • the dried precipitate was then subjected to calcination at 500 ° C in the presence of air.
  • composition of the calcined product defined as metal oxides and carbonate equivalents expressed as CO2, is given below in percentage by weight: La2O3 63.6%, BaO: 7.2% and CO2: 29.2%.
  • Example 2 The operation was carried out as indicated in Example 1, starting from an aqueous solution of barium cations and lanthanum cations prepared by dissolving 0.278 mole of BaCl2, 2H2O and 0.139 mole of LaCl3, 6H2O in 1 liter of distilled water.
  • composition of the product obtained by calcination of the dried coprecipitate defined as metal oxides and carbonate equivalents expressed as CO2, was as follows in percentage by weight: La2O3: 55%, BaO: 27% and CO2: 18%.
  • An aqueous solution of barium cations and lanthanum cations was prepared by dissolving 0.6 mole of BaCl2, 2H2O and 0.2 mole of LaCl3, 6H2O in 1 liter of distilled water.
  • An aqueous precipitating solution was also prepared by dissolving 3.2 mole of NaOH and 8 ⁇ 10 ⁇ 3 mole of Na2CO3 in 1 liter of distilled water.
  • the aqueous solution of cations was introduced continuously, simultaneously and separately, operating at room temperature and with stirring.
  • the aqueous precipitating solution for precipitating the cations in the form of a coprecipitate of carbonate and of hydroxycarbonate, the flow rates of the solutions introduced into the flask being adjusted to maintain the pH of the reaction medium resulting from the contacting of the said solutions with a constant value equal to 13.
  • the reaction medium containing the coprecipitate was then brought to 80 ° C. and maintained at this temperature, still with stirring, for a period of 5 hours.
  • the coprecipitate was then separated from the reaction medium by filtration, then washed with distilled water until complete elimination of the chlorides and finally dried at 60 ° C.
  • the dried precipitate was then subjected to calcination at 500 ° C in the presence of air.
  • the calcined product formed consisted of a barium and lanthanum oxycarbonate.
  • composition of said calcined product defined as indicated in Example 1, was as follows, in percentage by weight: La2O3: 38.8%, BaO: 53.9% and CO2: 7.3%.
  • An aqueous solution of magnesium cations and samarium cations was prepared by dissolving 0.75 mole of MgCl2, 6H2O and 0.25 mole of SmCl3, 6H2O in 1 liter of distilled water.
  • An aqueous precipitating solution was also prepared by dissolving 1.6 moles of NaOH and 0.01 moles of Na2CO3 in 1 liter of distilled water.
  • the reaction medium containing the coprecipitate was then brought to 70 ° C. and maintained at this temperature, still with stirring, for a period of 18 hours.
  • the coprecipitate was then separated from the reaction medium by filtration, then washed with distilled water until complete elimination of the chlorides and finally dried at 60 ° C.
  • the dried precipitate was then calcined at 500 ° C in the presence of air.
  • the resulting calcined product consisted of a magnesium and samarium oxycarbonate.
  • composition of said calcined product defined as indicated in Example 1, was as follows, in percentage by weight: Sm2O3: 48.7%, MgO: 34.4% and CO2: 16.9%
  • An aqueous solution of barium cations and samarium cations was prepared by dissolving 0.75 mole of BaCl2, 2H2O and 0.25 mole of SmCl3, 6H2O in one liter of distilled water.
  • An aqueous precipitating solution was also prepared by dissolving 10 moles of NaOH and 0.12 moles of Na2CO3 in 1 liter of distilled water.
  • the aqueous solution of cations was introduced simultaneously and separately, operating at room temperature and with stirring, on the one hand and the precipitating aqueous solution on the other hand.
  • the flow rates of the solutions introduced into the flask being adjusted to maintain the pH of the reaction medium resulting from the contacting of said solutions at a constant value equal to 13 .
  • the reaction medium containing the coprecipitate was then brought to 70 ° C. and maintained at this temperature, still with stirring, for a period of 18 hours.
  • the coprecipitate was then separated from the reaction medium by filtration, then washed with distilled water until complete elimination of the chlorides and finally dried at 60 ° C.
  • the dried precipitate was then calcined at 500 ° C in the presence of air.
  • the resulting calcined product consisted of a barium and samarium oxycarbonate.
  • composition of said calcined product defined as indicated in Example 1, was as follows, in percentage by weight: Sm2O3: 53.3%, BaO: 25% and CO2: 21.7%
  • a device comprising a tubular reactor mounted in an oven provided with a temperature control system, one end of the reactor being connected to a gas mixture supply pipe equipped with a flow meter and the other end of the reactor being connected to a condenser maintained at 0 ° C. and itself connected to a sampling system of a chromatographic analyzer.
  • a mixture of 2 g of the chosen catalyst, said catalyst being in the form of particles having a particle size of 1 to 2 mm, and quartz grains in a volumetric ratio of catalyst to quartz equal to 1: 2 was placed in the reactor tubular and held in place in said reactor by quartz lamé pads.
  • the catalytic mixture occupied a position in the reactor placing said mixture substantially in the middle of the furnace heating zone when the reactor was in place in the furnace.
  • the reaction gas mixture resulting from the conversion was cooled in the condenser, then directed to the sampling system of the chromatographic analyzer for qualitative and quantitative analyzes.
  • the comparison of the results appearing in the table shows the improved performances of the catalysts according to the invention.
  • the catalyst prepared in Example 1 leads to a slightly higher methane conversion rate with a selectivity for C hydrocarbons. + 2 substantially improved compared to that obtained by using product A as catalyst, that is to say a product containing the barium and lanthanum elements in the form of oxides.
  • the catalysts according to the invention lead to substantially higher conversion rates of methane than those obtained under comparable conditions with catalysts consisting of barium carbonate (product B) or lanthanum carbonate (product C), without that the selectivity in hydrocarbons is affected.
  • the catalysts according to the invention make it possible to work with high space velocities.

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Claims (21)

1. Verfahren zur Herstellung eines Katalysators, der wenigstens ein Metall der Gruppe der Lanthanide und wenigstens ein Erdalkalimetall in Form von Carbonaten und/oder Hydroxycarbonaten enthält, dadurch gekennzeichnet, daß man eine wässerige Phase, die Kationen wenigstens eines Metalls der Gruppe der Lanthanide mit den Ordnungszahlen 57 und 59 bis 71 des Periodensystems und Kationen wenigstens eines Erdalkalimetalls in Lösung enthält, mit einer ausreichenden Menge einer Carbonationenquelle und gegebenenfalls einer Hydroxidionenquelle zur Bildung eines Copräzipitats von Carbonaten und/oder Hydroxycarbonaten der genannten Metalle mit wenigstens 5 Gew.-% Carbonaten und Einstellung des pH's des Reaktionsmediums auf einen Wert von über 8, umsetzt und das Copräzipitat vom Reaktionsmedium abtrennt, es wäscht, trocknet und danach bei einer Temperatur zwischen 400 und 1000°C glüht.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man vor der Abtrennung des Copräzipitats vom Reaktionsmedium das das Reaktionsmedium enthaltende Copräzipitat bei einer Temperatur von 60 bis 150°C während 30 Minuten bis 30 Stunden, vorzugsweise 2 bis 20 Stunden, hält.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß das Metall oder die Metalle der Gruppe der Lanthanide, ausgewählt ist bzw. sind unter Lanthan, Praseodym, Neodym, Samarium, Europium, Gadolinium, Terbium, Dysprosium, Erbium, Holmium, Thulium, Ytterbium und Lutetium.
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß das (die) Erdalkalimetall(e) ausgewählt ist (sind) unter Beryllium, Magnesium, Calcium, Strontium und Barium.
5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß der Gewichtsprozentgehalt L des Metalls oder der Metalle der Lanthanide und T des Erdalkalimetalls bzw. der Erdalkalimetalle, das (die) in der wässerigen Phase vorliegenden Kationen liefern, bezogen auf die Gesamtheit der Metalle, so gewählt ist, daß 6 ≦ L ≦ 98 und 2 ≦ T ≦ 94, wobei L + T = 100%.
6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß die wässerige Phase neben den Kationen des Metalls oder der Metalle der Lanthanide und den Kationen des Erdalkalimetalls bzw. der Erdalkalimetalle auch noch zusätzliche Kationen eines oder mehrerer anderer Metalle, insbesondere Scandium, Yttrium und Lithium, in Lösung enthält.
7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, daß die Menge der zusätzlichen Kationen bis zu 30%, vorzugsweise bis zu 15% des Gesamtgewichts der Kationen des Metalls oder der Metalle der Lanthanide und den Kationen des Erdalkalimetalls bzw. der Erdalkalimetalle ausmacht.
8. Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß die Carbonationenquelle ausgewählt wird unter Alkalimetallcarbonaten, Ammoniumcarbonat und quaternären Ammoniumcarbonaten.
9. Verfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß die Hydroxidionenquelle ausgewählt wird unter Alkalimetallhydroxiden und quaternären Ammoniumhydroxiden.
10. Verfahren nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß das Verhältnis der Carbonationenquelle oder die Verhältnisse der Carbonationenquelle und der Hydroxidionenquelle so gewählt werden, daß das bei der Umsetzung dieser Ionen mit den in der wässerigen Phase vorliegenden Kationen erhaltene Copräzipitat 5 bis 100 Gew.-% Carbonate enthält und der pH des Reaktionsmediums auf einen Wert zwischen 9,5 und 13,5 eingestellt wird.
11. Verfahren nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, daß die in der wässerigen Phase vorliegenden Kationen ausschließlich mit einer Carbonationenquelle umgesetzt werden, die dieser in Form einer wässerigen Lösung zugesetzt wird, wobei die Zugabe in einer oder mehreren Portionen oder auch kontinuierlich erfolgt.
12. Verfahren nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, daß die in der wässerigen Phase vorliegenden Kationen mit einer Hydroxidionenquelle und einer Carbonationenquelle umgesetzt werden, wobei diese Quellen in Form wässeriger Lösungen nacheinander, im Gemisch oder gleichzeitig und getrennt, der die Kationen enthaltenden wässerigen Phase zugesetzt werden, wobei jede Zugabe in einer oder mehreren Portionen oder kontinuierlich erfolgt.
13. Verfahren nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, daß die Umsetzung der in der wässerigen Phase vorliegenden Kationen mit den Carbonationen oder den Carbonat- und Hydroxidionen durch kontinuierliches Mischen der die Kationen enthaltenden wässerigen Phase mit einer alkalischen wässerigen Phase, welche die Carbonationenquelle oder diese und die Hydroxidionenquelle in Lösung enthält, in geeigneten Konzentrationen durchgeführt wird, wobei die Durchflußmenge der wässerigen Phasen so gewählt wird, daß das gebildete Copräzipitat wenigstens 5 Gew.-% Carbonate enthält und der pH des Reaktionsmediums während der Copräzipitation konstant bleibt und über 8 und vorzugsweise zwischen 9,5 und 13,5 liegt.
14. Verfahren nach einem der Ansprüche 1 bis 13, dadurch gekennzeichnet, daß das vom Reaktionsmedium abgetrennte Copräzipitat mit destilliertem oder entmineralisiertem Wasser bis zur vollständigen Entfernung der störenden Ionen gewaschen wird.
15. Verfahren nach einem der Ansprüche 1 bis 14, dadurch gekennzeichnet, daß das gewaschene Copräzipitat bei Temperaturen zwischen 60 und 90°C getrocknet wird.
16. Verfahren nach einem der Ansprüche 1 bis 15, dadurch gekennzeichnet, daß das getrocknete Copräzipitat bei Temperaturen zwischen 450 und 800°C geglüht wird.
17. Verfahren zur oxydativen Umwandlung von Methan zu höheren Kohlenwasserstoffen und insbesondere zu C₂-Kohlenwasserstoffen durch Leiten eines Methan und Sauerstoff enthaltenden Gasgemisches über einen Katalysator bei einer Temperatur zwischen 600 und 1100°C, dadurch gekennzeichnet, daß der Katalysator nach dem Verfahren nach einem der Ansprüche 1 bis 16 erhalten wurde.
18. Verfahren nach Anspruch 17, dadurch gekennzeichnet, daß das Molverhältnis von Methan zu Sauerstoff in dem mit dem Katalysator kontaktierten Gasgemisch zwischen 1 und 20 und vorzugsweise zwischen 2 und 10 liegt.
19. Verfahren nach Anspruch 17 oder 18, dadurch gekennzeichnet, daß die Umwandlungstemperatur zwischen 700 und 900°C liegt.
20. Verfahren nach einem der Ansprüche 17 bis 19, dadurch gekennzeichnet, daß die Volumengeschwindigkeit des Gasgemisches aus Methan und Sauerstoff im Kontakt mit dem Katalysator, ausgedrückt in Liter Gasgemisch pro Gramm Katalysator und Stunde, zwischen 3 und 1000 und vorzugsweise zwischen 5 und 300 liegt.
21. Verfahren nach einem der Ansprüche 17 bis 20, dadurch gekennzeichnet, daß die Umwandlung unter Drükken zwischen 1 und ca. 50 bar und vorzugsweise zwischen 1 und 20 bar durchgeführt wird.
EP89401840A 1988-06-29 1989-06-27 Verfahren zur Herstellung eines Katalysators, verwendbar für die oxydierende Umwandlung von Methan in hohe Kohlenwasserstoffe Expired - Lifetime EP0349419B1 (de)

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Application Number Priority Date Filing Date Title
FR8808766A FR2634398B1 (fr) 1988-06-29 1988-06-29 Procede de preparation d'un catalyseur apte a promouvoir la conversion oxydante du methane en hydrocarbures superieurs
FR8808766 1988-06-29

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EP0349419B1 true EP0349419B1 (de) 1992-02-05

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US (1) US5061670A (de)
EP (1) EP0349419B1 (de)
JP (1) JP2733588B2 (de)
AU (1) AU615091B2 (de)
CA (1) CA1326008C (de)
DE (1) DE68900812D1 (de)
ES (1) ES2030286T3 (de)
FR (1) FR2634398B1 (de)
WO (1) WO1990000086A1 (de)

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ES2030286T3 (es) 1992-10-16
WO1990000086A1 (fr) 1990-01-11
AU3879089A (en) 1990-01-23
CA1326008C (fr) 1994-01-11
FR2634398A1 (fr) 1990-01-26
FR2634398B1 (fr) 1990-09-07
US5061670A (en) 1991-10-29
DE68900812D1 (de) 1992-03-19
JPH03501100A (ja) 1991-03-14
JP2733588B2 (ja) 1998-03-30
AU615091B2 (en) 1991-09-19
EP0349419A1 (de) 1990-01-03

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